Removal of zeolytic alkali from gels



ug. 30, 1949. E. A. BODKIN REMOVAL 0F ZEOLYTIC ALKALI FRQM GELS Filed July- 24, 194e ATTORNE Patented Aug. 30, 1949 REMOVAL or zEoLYrio ALKALI FROM GELs Ernest A. Bodkin, Pitman, N. J., assignor to Sosony-Vacuum Oil Company, Incorporated, a corporation of New York Application July 24, 1946, Serial No. 685,834

1 Claim.

This invention relates to a process for treating inorganic oxide gels with aqueous solutions and to the treated products so prepared.

The preparation of inorganic oxide gels for such purposes as catalysis, adsorption and the like generally requires purification to remove matter foreign to the basic gel structure. The water soluble salts resulting from the reaction by which the gel is produced may be washed out quite readily with water, but gels formed by the use of water glass at pH values greater than about 2 to 3 normallyT contain such impurities as zeolytic sodium which cannot be adequately removed by water washing over any practicable period of time. The zeolytic impurities are removable by a base exchange reaction, substituting for the impurity, another ion or radical which is either desirable, innocuous or readily removable. The nature of the zeolytic constituents can be best understood by reference to exemplary compositions such as catalysts and desiccants.

A silica-alumina gel can be employed as a catalyst for the cracking of hydrocarbons in a cyclic process including a reaction stage in which the charge hydrocarbon is converted to a lower boiling hydrocarbon with concurrent deposition of a carbonaceous contaminant on the catalyst. The carbonaceous deposit seriously impairs the eiciency of the catalyst. Catalytic activity is then restored by burning the deposit in a regeneration stage and the catalyst is returned to the reaction stage. Alkali metals have a detrimental eiect on such catalysts in that the activity drops rapidly over a series of cycles, apparently because the alkali metal induces a change in the catalyst during the high temperature regeneration stage. The gel is generally formed by reaction of dilute Water glass with aluminum sulfate or sodium aluminate solution and contains substantial quantities of zeolytic sodium. The sodium ions may be largely replaced by base exchange with metal salts to introduce a desirable metal ion such as aluminum, zirconium, beryllium, etc., with aqueous ammonia which can later be decomposed by heat to evolve ammonia gas; or with hydrogen ions from acid solutions.

)Similar considerations apply to the manufacture of desiccants. Silica gel formed at pH `1 or thereabouts may be Washed free of substantially all impurities, including sodium, by passing water through a bed of hydrogel granules for two or three days. However, the modern techniques of gel formation to obtain smooth surfaced particles require a hydrogel having a pH value of 2 or greater for economical operation since the short gelation times are only obtainable at these higher pH values. The gelsv so formed contain sodium which is not removed by water washing over a practicable period of time. Theoretically, it may be postulated that water washing will exchange hydrogen for sodium in the gel; but, so far as is known, this has not been demonstrated. If such exchange is possible, the low hydrogen ion content of water alone makes vit likely that very long periods of time would be required; perhaps a year or more of washing.

The present invention relates to a process for the preparation of valuable dry gels from inorganic oxide hydrogels by base exchanging the hydrogel with a Weak acid such as acetic, boric, citric, carbonio and the like. Strong acids tend to dissolve out metal oxides such as alumina and the likel which are essential to cracking catalysts and are advantageously employed in the manufacture of desiccants and the like in small amounts to reduce breakage during processing and drying. This effect can be overcome by using dilute solutions having pH values on the order of 2 or more, but the amount of hydrogen ions available for base exchange in such case is so small that inordinately long washing periods are required. The present invention, utilizing aqueous solutions of weak acids gives pH values suiciently low to avoid leaching out desirable metal oxides and also provides a source of available hydrogen as un-ionized acid which slowly ionizes as hydrogen ions are consumed bybase exchange.

The action of these weak acids may be capable of explanation based on the size of the pores in the gel under treatment. The rate of diffusion into the ne capillaries of the gel is necessarily very slow. If a strong acid is used at such dilution as to avoid leaching out of desirable metal oxides, the number of hydrogen ions entering a capillary over a practicable period of time is insulilcient to remove a suitable amount of alkali metal ions by base exchange. By way of contrast, a more concentrated solution of a weak acid may be used without seriously affecting the concentration of desirable metal oxide in the gel. This solution penetrates the pores and, as hydrogen ions are consumed by base exchange, the concentration thereof in the solution is maintained by ionization of the weak acid. In this manner, it may be assumed that the weak acid is capable of supplying suli'icient hydrogen ions to remove alkali metals by base exchange without using a solution of sufficient acidity to leach out polyvalent metal oxides forming part of the gel structure.

The weak acids used according to the present invention are those having ionization constants not substantially greater than Ddd-3. The acidity of the solution should not be substantially greater than pH 2.5 and is preferably below pH 3.5. The step of base exchange with a weakA acid may be part o a complete process in which the gel is also washed with another base exchange agent such as aqueous solutions of ammonium and polyvalent metal compounds. Improved results are thereby frequently obtained. For some reason that is not understood, base exchange with two dissimilar base exchange agents in series is often more eicacious than a treatment of comparable nature (as to time of treatment and concentration of` treating solution)` with either ofthe base exchange agents.

The process. of treating gels'` for removal of al,- lsiali metals byl base exchangeY according to the present invention is applicable to ,hydiogels and alsoto. gels which have been previously dried. As to the latter, itis desirable that-measuresbe taken tol prevent: breakage of the dry gel on immersion in water or aqueous treating solutions This may be,` accomplished by wetting the gel -rst with a liquid which` does not induce breakaga such as hydrocarbon liquids, alcohol, concentrated sol-utions of organic compounds: such as sugar., and the like. The non-breaking liquid is then-,replaced by the aqueous treating liquid in such-manner as may be necessary es byimmersinggel; Wet with water; misc-ible liquid directly' inA water or the treating solution. Gels wet, with water immiscible Liquids must be. transferred to water in stages;- fgor exampleLkerosene to acetone to water.

An even more satisfactory method for wetting toV impregna-te the dry gel with a. gas which is readily taken upf by aqueous solutions, such as steam, carbon dioxide or ammonia., 1 -he latter two are particularly desirable when the,r gel@ is. to bef treated with carbonio. acid or ammonium hydroxidc-z, respectively. The saturation or the gel with the gas corresponding to the. aqueous treating; solution appears to condition the gel and render it more amenable to treatment.

The invention is well adapted to preparation of eel type cracking catalysts composed-primarily of silica and, one or more-polyvalentmetal. oxides; and;` the detail-ed description herein will bev directed to, production oi suchv materials,y it. being understood that the principles: hereof." are equally applicable to all gel-type materials regardlessl of theirx intended use as desiccants.. catalysts. adsorbents, etc.

EXAMPLE I One,7 speci: embodiment. ofA the invention contemplates reduction i-n alkali metal content of. a silica alumina4 cracking catalyst formed byy reactionroi, water-glass and aluminum sulfate; for example, as; disclcsed` in; S. Paten-t; N o.. 23Std/16.

issued September 18, 1945, to Milton M. Marlsic. The gel is Washed with carbonio acid, aqueous ammonia and water in series. If the gel has been previously dried, it is first impregnated with carbon dioxide and then immersed in the treating solution. Apparatus for that process is shown in the annexed drawing which shows, diagrammaticallyapparatus for continuous countercurrent washing of gel in a plurality of vessels in series.

A plurality of washing vessels, numbered I to I2, inclusive, are provided for contacting the gel with aqueous treating and washing agents. The effect of countercurrent contact between gel and aqueous medium is obtained by passing water in series through a number of vessels, say ten, containing gel which has been in the Washing stream for successively shorter periods. Periodically, the rst washing vessel (containing gel which has been in the washing cycle for the greatest period of time) is taken out of the cycle, the succeeding vessel is made the first and a vessel of unwashed gel is added at the end.

In a typical operationy bead hydrogel, prepared according to the above mentioned Marisic patent, is washed in a series of ten vessels, say numbers 2 to, th inclusive, oi the drawing. The gelin vessel 2 has been in the washing cycle the greatest period of time, with the succeeding vessels containing gel of successivelyV lesser age. In each vessel, aqueous wash liquid is supplied at the top and withdraw-n at the bottom.

Fresh wash water is supplied to. manifold I3 havin-gA twelve bra-noliv lines to the twelve vessels, each fitted with a suitable valve I4. In the operation stated, valve I4 for vessel 2v is open and the other valves I4 are closed. Transferlines oontrolled by valfves i5 connect a discharge at the bottom of each vessel vwith the inlet at the top ofthe succeeding vessel. The valve t5 preceding vessel 2; is closed while those following vessels 2 and 3 are open with the valve I5,- foll-owing vessel dfc-losed'. Thus, the fresh water ows in series through vessels 2 to 4 and is then diverted to header I6 for supplying anammonia mixing tank III. A valve I8v controls ilow from the discharge of each of the vessels to the header I6, and in the present` instance valve I8 associated with vessel 4 is openandthe remainder of the valves i8I are closed. In mixer Il, concentrated aqueous amnionia isadded to the circulating waterv to provide a solution containing 5% byweight of NH4OH. Suitable agitation isy provided,y as, by air injected frorn-A pipe I9.

The ammonia solution prepared in:A mixer I'F is transferred to` manifold 20 which communicates with. eachvof the vessels through lines controlled by valves 2 I of; which onlyv the valve; 2IAv associated with vessel 5 is open. Valves, t5 following vessels 5, and 61 are open to. permit the ammonia base exchangeY solution to flow in series through vessels 5, 6. and 1.., The liquid withdrawn from vessel 'I passes through-v open valve 2,2 to line 2-.3I supplying a oarbonator 2 4, Carbon dioxide is injectedto the bottom, of carbonator 24,. asy a, ine dispersion and the bubbles;A of gas are absorbedbv the. aque.- o,us ammonia. to neutralize the same and acidity it to. a, pH value of about, 4, to 4.5. The oarbonator 2L, is a. closed vessel vented to. a mercury seal, 25 adjusted. to a. carbonator pressure ot about two pounds, per square inchY (gauge),

The, acidied solution is. transferred from the bottom of carbonator 24 to a manifold., 26 sup,- plying. vessel 8 through openvalve Z-I` associated witnsaid vessel-8. The valves 'L5 4io1lowins,vessels 8, 9 and l0 being open, the carbonio acid solution ows through vessels 8, 9,l I and Il in series and is lthen passed through open valve 28 to a waste Dipe29.

The gel is washed with the solutions indicated above over a total period of 25 hours, two and one'- half .hours at each of the ten' stages. `-The oldest gel in the series is removed upon completion of its washing period and the fresh water diverted to the next succeeding vessel, each vessel in the series being'moved up one place by manipulation of valves and a body of fresh gel being placed at the end of the series. The two vessels out of the washing cycle are emptied and relled, being ready to assume the last place inthe cycle at 'the proper time.

' The sequence of treating gel so obtained is very favorable to a high degree of sodium removal and a low breakage of the gel on drying. It has been found that rapid change in environment of fresh hydrogel by immersion in a liquidhaving a composition varying substantially from the composition of the water contained in the pores lof the gel results in excessive breakage of the gel upon drying. By the process described above, fresh hydrogel is contacted with aqueous liquid which has passed through and taken up soluble matter from a number of beds of hydrogel. The pH value of the wash water is also affected by passing through beds of gel and approaches that of the water in the gel at the last bed in the washing cycle. There is a sharp change in pH of Wash water between vvessels onv either side of a step of adding something (e. g. lammonia or carbon dioxide) to the water. However, by the time a vessel of hydrogel passes through this transition, it has been aged in aqueous media to a degree which renders the sharp change innocuous. Y In the order of treatment of. a given -bed of hydrogel, the gel is washed in succession with an acid solution containing hydrogen ions and generally a small amount of ammonium ions vwhich lower the sodium content of the gel by zeolytic base exchange; replacing the sodium with hydrogen and, perhaps-some ammonium radicals. The hydrogel is then scavenged of the major portion of the remaining sodium by zeolytic base exchange in an alkaline solution containing ammonium ions. The treated gel is then washed with progressively purer ywater until it is receiving fresh water directly and after a period in that condition is ready f or drying and such activation as may be desired for the use for which it is intended.

The order of treatment with carbonio acid and ammonia described above may be reversed, treating first with ammonia, followed by treatment with carbonio acid as scavenging agent. The order described above and shown in the drawings is preferred because ammonia appears to be a more effective scavenging agent.

EXAMPLE II The same equipment and sequence of steps is employed in the treatment of dried gel, except that the gel is rst treated to condition it for the treatment. When the carbonio acid wash is first, the gel is swept with a slowly moving stream of carbon dioxide under any suitable pressure before immersion in carbonio acid. Since increased pressure appears to yield no real advantage, a pressure is generally used which exceeds atmospheric by a suiiicient margin to induce the desired rate of iiow. The carbon dioxide replaces the air or other gas in the gel pores and the displaced gas is swept out of the bed of gel in the stream of carbon dioxide. The tendency to breakage on wetting may be overcome by the use of any gas readily soluble in water but use of a gas corresponding to that dissolved in the treating medium is'preferred. The advantages intime of treatment for the desired degree of base exchange may be capable of explanation on an assumption that the gas becomes elective for base exchange by reason of water adsorbed in the gel; however, this theory cannot be proven on the basis of available data.

In the same manner, dry gel is first treated with ammonia gas when the order of the treating solutions is reversed. The ammonia treated gel is then immersed in a solution containing ammonium ions and carried through the treatment outlined above.

The effect of treating gels with weak acids is demonstrated by the following examples describingtreatment of hydrogel beads prepared according .to the disclosure of the above noted Marisic patent.

v. EXAMPLE III The hydrogel was base exchanged with aluminum sulfate solution, water washed and then scavenged for residual sodium by washing with carbonio acid. In the scavenging operation, carbonic acid was prepared by flowing the wash water downwardly through a vertical vessel and bubbling carbon dioxide into the bottom. The system was maintained under a pressure of about two inches of mercury. The carbonio acid solution (pH 4.1) was passed downwardly through a bed containing four liters of gel at ten cc. per minute for about 11/2 days at room temperature. The gel was then dried in an atmosphere of circulating superheated steam at 250 F. and then heated in a muflle to 1050 F. at the rate of 3 F. per minute. After tempering at 1050 F. for one hour, the gel was found to be an efficient catalyst for the cracking of hydrocarbons. The sodium content of the finished catalyst was 0.11% by weight This constitutes removal of more than 20%' of the sodium in the gel before scavenging.

EXAMPLE IV l Two samples of fresh gel which had received no treatment for removal of soluble matter and zeolytic sodium were washed for 26 and 45 hours respectively with carbonio acid of pH 3.9 to 4.1. The fresh gel as submitted to treatment contained 13.3% sodium by weight (dry basis). The two base exchanging treatments described reduced this to 0.90% and 0.4%, respectively.

EXAMPLE V The process is also effective in connection with gel which has been previously dried. A sample of finished bead cracking catalyst prepared according to the said Marisic patent, including base exchange with aluminum sulfate solution, water washing, drying and tempering at l F. was divided into five portions. Portion 1 was used on a basis of comparison. Portions 2 and 3 were subjected to treatment with carbon dioxide gas passed therethrough for 1 hour at room temperature. They were then washed at room temperature with 11,000 cc. of aqueous medium at room temperature for three days (2.5 cc. per minute). Portion 2 was treated with water, while portion 3 was treated with a saturated aqueous solution of carbon dioxide (pH about 4). Portions 4 and 5 were similarly handled in ammonia treatments; i. e. NH3 gas for one hour followed by treatment of portion 4 with water andv portion 5 with 1%- ammonium. hydroxide solution at the rate mentioned above. The following-table shows the results obtained. Signicantly, the breakage was" substantially less in the carbonic'acid treated pox.'- tion than in the corresponding water treated por. tion.

Table 1 Table 2 Sodium per w' P t V l Gas Treat- Aqueous f. me Percent Na P ortlon ment Wh cetyigtasign ample scavenging Solution ggsle by wt' 0. 24 4&1 .24 0.18, 60 g HaBOa/MOO C0 H20 50. 5 .13 o. ne 4o g B3B 0./1400 ce 50.0 1c 0.19 g. HzBOg/MOO C0 H:O 49.4 .18 0.11 1.3% CHaCOOH, 47. 5 .12

EXAMPLE. VI

A sample of bead alumina-silica catalyst fory cracking` hydrocarbons was prepared in con ventional manner for comparison with the sucoeeding examples. The gel was formed at pH 8.4 with '7.2% by weight of solids in the gel. After aging four days in Water at room temperature, 3500 cc. of the gel was treated with 1400 cc. of solution containing 3 theoretical Weights of aluminum' sulfate for eight hours. The treatment was repeated and the gel was then dried slowly and tempered at 1100 F. Its effectiveness as a cracking catalyst and other properties are shown below in Table 2.

EXAMPLE VII EXAMPLE VIII Gel (3500 cc.) which had been aged two days in Water at room temperature was washed twice for ve hours with aluminum sulfate as in Example VI. This gel was then treated for 24 hours with 40 grams of boric acid in 1400 cc. of water.

EXAMPLE IX The treatment of Example VIII was repeated,

using 20 grams of boric acid in 1400 cc. of water for scavenging.

EXAMPLE X A 3500 cc. samplev of fresh gel was subjected to two treatments of six hours each with the aluminum sulfate solution of Example VI. It was zeolytlcalkali metal. from said gel.

ERNEST A. BODKIN.

REFERENCES CITED 'I he following references are. of record in the file of this; patent:

UNITED STATES PATENTS Number Name Date 1,83-135'73 Liebknecht Nov. 10, 1931 1,835,420 Neundlinger Dec. 8, 1931 2,331,338 Michael et al. Oct. 12, 1938 2,197,862 Hyman Apr. 23, 1940- 2,229,353 Thomas Jan. 2l, 1941 4.0 2,283,172V Bates May 19, 1942 2,326,323 Benedict Aug. 10, 1943 2,346,657 Bloch et al. Apr. 18, 1944 2,385,217 MariSc Sept. 18, 1945 2,390,272 Riesmeyer Dec. 4, 1945v 221063614: Lee Aug. 27, 1946 2,411,806 Riesmeyer et al. Nov. 26, 1946 FOREIGN PATENTS Number Country Date 211,564 Great Britain May 25, 192'? 595,859 Germany Apr. 23, i934 OTHER REFERENCES Certificate of Correction Patent No. 2,480,628 August 30, 1949 ERNEST A. BODKIN It is hereby eertied that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 6, line 56, for 0.4% read 0.41%;

same may conform to the record of the case in the Patent Ofce. v

Slgned and sealed this 14th day of February, A. D. 1950.

[SEAL] THOMAS F. MURPHY,

Assistant Uammzssz'oner of Patents. 

